Insecticidal composition containing a polychloro p-menthane



Patented Mar. 27, 1951 INSECTICIDAL COMPOSITION CONTAINING A POLYCHLORO 'p-MENTHANE William D. Stonecipher, Newark, Del., assignor to Hercules Powder Company, Wilmington, Del., a corporation of Delaware No Drawing. Original application August 4, 1945,

I Serial No. 609,019. Divided and this application June 23, 1950, Serial No. 170,026

2 Claims. (older-e30) l 1 a This invention relates to an insecticidal composition and more particularly to an insecticidal composition containing a polychloro monocyclic terpene as the toxic ingredient.

' insecticide into the chamber the flies were placed in an observation cage containing a wad of cotton wet with a concentrated sugar solution. At the end of 24 hours the number of dead and mori- Among the more commonly used insecticidal 5 bund flies were counted. All tests were carried toxicants are the naturally occurring products, out at 80-90 F. and 50-70% relative humidity. pyrethrum, rotenone and nicotine. These The results of the analysis for chlorine content natural products have the very great disadvanand of tests made on 5% solutions in Dec-Base tage of not being uniform in their insecticidal of the above 6 polychloro p-menthanes are given activity. Many synthetic products have been 0 in the following table. The data is an average suggested in the past as substitutes for these of a series of tests made on each solution. toxicants, however, they are usually lacking in v one respect or another. They do not have a high tests on mes enough killing power and must be used in cons A centrations which cause irritation to the user, or 3mi Percent Per Cent o. 'r.1.' if they are sufficiently toxic, they are also toxic Timein Chlorine 2f? gga to forms of animal life other than insect pests.

Now in accordance with this invention it has been found that insecticidal compositions con- 3 gig taining as a toxic ingredient a polychloro mono- 11.23 64.3 100 +49 cyclic terpene, having a chlorine content of from 22:1 32 about 50% to about 75%, possess a high degree 19.5 71.1 91 of insecticidal activity.

; The following examples will illustrate the EXAMPLE 2 1 l' preparation of these polychoron onocycac ter 25 I one part of p menthane dissolved in 5 parts penes and the insecticidal activity of compo sitions ontaining them. of carbon tetrachloride was placed in a chlorination vessel and exposed to ultraviolet illumina- EXAMPLE 1 tion. Chlorine was passed into the agitated mixture at a rate that allowed for maximum absorp- -One part of dipentene dlSSOlVGd in 5 parts of tion. After 11 hours of chlorination samples carbon tetrach oride was placed in a chlorination were taken every 2 to 4 hours, a total of 5 samples vessel and exposed to ultraviolet illumination. g taken The carbon tetrachloride was Chlorinewas passed into. the agitated l moved from each sample by distilfation under at rate that allowed for max'mum absorptlon reduced pressure. The material which remained of the chlorine. After 8 hours of chlorination, 45 in each case Was a viscous yellow liquid which samples were taken every 2 t9 3 hours a tntal of was analyzed for chlorine content. The results 6 samples being removed. The carbon tet aof testing 5% solutions in Dee-Base of each of chloride was removed from each sample by dlsthese polychloro p menthanes for their tillation under reduced pressure and a viscous cidal activity against house flies by the bell jar yellow liquid remained in each case. 40 method are given in the following table The 6 ch orinated dipentene materials, of different chlorine content, were tested for the in- Bell tests files secticidal activity against house flies. In this and the following examples, the test for insectip P C t Per Cent L cidal activity against house flies was made in the Till? ifi ff Dead in fferfollowing manner and is referred to in this speci 24 fication as the bell jar method.

Approximately 100 five-day old flies (Musca 5 88 +2? domestica) were placed in a bel jar and a pre- 18 6 7:5 100 145 determined quantity of the insecticide to be tested was atomized into the be l jar. The quantity of insecticide used was equal to the amount of an Offlcial Test Insecticide which was neces- EXAMPLE 3 sary to give a 30-55% kill and must be within 0 Apolychlorop-menthanecontaining61.8%chlothe limits of 0.25 to 0.35 cc. After spraying the rine,preparedbychlorinatingdipentene,wastested EXAMPLE 4 The test in Example 3 was repeated except that a polychloro p-menthane containing 68.2% chlorine was used in combination with the isobornyl thiocyanoacetate. This combination had a -minute knockdown of 100%, and a 24-hour kill of 98% which corresponded to an O. T. 1;

difference of +53.

Any po'ychloro monocyclic terpene containing from about 50% to about 75%, and preferably from about 55% to about 70% chlorine, may be used as the toxic ingredient of the insecticide compositions of this invention. Chlo-inated monocyclic terpenes having a chlorine content of'less than 50% are so inactive as to be worthless as insecticides. In fact, such compounds as a monochloro terpene lack any appreciable degree of insecticidal activity. The same thing is true for polychloro p-menthanes having a chlorine content above 75%, as the insecticidal activity decreases greatly as the chlorine content is raised above this point.

The polychloro monocyc'ic terpenes are prepared by chlorinating any monocyclic terpene, for example, polychloro p-menthanes are obtained by chlorinating dipentene, terplnolene, terpinene, p-menthene an p-menthane. The chlorination of the monocyclic terpene may be carried out in the presence or absence of a solvent. Lower temperatures are maintained during the chlorination if a solvent is used; however, in some instances it is preferafile to use high temperatures in order to obtain the desired degree of chlorination. Suitable solvents for the chlorination are chloroform, carbon tet achloride, pentachloroethane, etc. A chlorination catalyst may be used if desired, ultraviolet light being particularly efiective.

The insecticidal compositions of this invention may be made up of the polychloro p-methane admixed with any type of diluent. If a liquid spray is desired, the polychloro p-menthane may be dissolved in any convenient solvent, such. as kerosene or Dec-Base, or it may be dispersed in water to form aqueous sprays. Insecticidal dusts may be prepared by placing the polychloro pmenthane on a diluent or carrier such as powdered carbon, kieselguhr, bentonite, pyrophyllit etc.

For many purposes it may be desired to use the polychloro p-menthane in combination with other insecticidal toxicants. Many toxicants have a very high knockdown in relatively dilute solutions, but higher concentrations must be used in order to obtain the desired degree of kill. Due

.to the high degree of killing power which the polychloro p-menthanes possess, these compounds may be added to such toxicants, thereby enabling the use of much more dilute solutions than would otherwise be possible. Toxicants with which these polychloro p-menthanes may be combined include such compounds as rotenone, pyrethrum and organic thiocyanates such as alkyl thiocyanates, thiocyano ethers such as fi-butoxy-B'-thiocyanoethyl ether, and terpene thiocyanoacylates such as isobornyl thiocyanoacetate, fenchyl thiocyanoacetate and isobornyl a-thiocyanopropionate.

As may be seen from the foregoing examples, the polychloro p-menthanes have a high degree of insecticidal activity. Thus the insecticidal compositions of this invention may contain any amount of the polychloro p-menthane that is efiective against the pest being killed. For use as a household fly spray, 1% to 10% in Dec-Base may be used. However, for killing many types of pests it will be desirable to use much higher concentrations of these toxicants.

The ins cticidal compositions of this invention are useful in combatting flies, mosquitoes, roaches, moths, and many other pests.

This application is a division of my copending application, Serial No. 609,019, filed August 4, 1945.

What I claim and desire to protect by Letters Patent is:

1. An insecticidal composition comprising anaqueous dispersion of a polychloro p-menthane containing from about 50% to about 75% of chlorine.

2. An insecticidal composition comprising an aqueous dispersion of a polychloro p-menthane containing from about to about of chlorine.

WILLIAM D. STONECIPHER.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Date Bender Aug. 13, 1935 

1. AN INSECTICIDAL COMPOSITION COMPRISING AN AQUEOUS DISPERSION OF A POLYCHLORO P-MENTHANE CONTAINING FROM ABOUT 50% TO ABOUT 75% OF CHLORINE. 